JPH09175931A - Microparticles coated with lamellar phase based on silicone surfactant and composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent microparticles which can be used in a locally applicable composition for treating skins, mucous membranes, scalps and hairs by lamella-coating a polymer having an oily phase with a specific silicone surfactant. SOLUTION: In microparticles with a particle size of 10-1,000nm, prepared by lamella-coating of a polymer containing an oil phase, the lamella coating is carried out using at least one of silicone surfactants bearing at least one of oxyethylenated and/or oxy-propylenated chains. The silicone surfactant is preferably a compound of formula I (R1 to R3 are an alkyl; R4 is H, an alkyl; A is 0-200; B is 0-50), formula II (A is 20-105; B is 2-10) and formula III (A' and y are each 10-20). The microparticles particularly have the particle size of 10-60nm. The polymer is preferably poly-L-lactides or polycaprolactones.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to fine particles (nanoparticles) having a lamellar coating composed of a silicone surfactant, and compositions using the same, particularly skin, mucous membranes, nails, scalp, and / or Alternatively, it relates to a composition for topical application for treating hair.

[0002]

In the fields of cosmetics and dermatology,
The application of these active agents entrapped in microspheres to the skin in order to improve the effect of the active agents is described, for example, in EP-A-557489, EP-A-447318.
And International Patent Publication No. 93/25195. These small spheres are particularly fine particles of a polymer and have a small diameter of the order of 10 to 1000 nm, so that they penetrate well into the upper layer of the epidermis. The term microparticles is meant to include "nanospheres" and "nanocapsule". “Nanospheres” refer to microparticles consisting of a porous polymer matrix that has adsorbed and / or adsorbed an active agent, and “nanocapsules” refer to microparticles consisting of a polymer film containing an oily core.

[0003]

When microparticles are incorporated into a composition, the active agent is frequently released into the composition. In particular, in the case of nanocapsules, when mixed with a composition containing an oil phase, such as an emulsion, the active agent contained in the oily core diffuses into the oil phase of the composition. The premature release of active agent into the composition eliminates the effect of encapsulating the microparticles.

To remedy this drawback, it is known to coat the microparticles with a lamellar phase. In the past, lamellar coatings based on lecithin have been used in order to obtain coatings that are almost leakproof, which are described in EP-A-447318. In practice, however, lecithin has the drawback of being sensitive to oxidation, resulting in yellowing of the microparticles, giving compositions containing them an unpleasant appearance to the user.

Therefore, there is a need to provide microparticles that have a good lamella coating that is leak-free and does not have the above-mentioned drawbacks.

[0006]

Means for Solving the Problems and Embodiments of the Invention
The Applicant has unexpectedly found a lamellar coating which makes it possible to achieve this end.

In fact, the Applicant has found that the use of silicone surfactants makes it possible to obtain finer white particles which are less sensitive to oxidation. Furthermore, the use of silicone surfactants significantly increases the production of coated microparticles per hour. In fact, the presence of silicone surfactants reduces the foam formed during their manufacture.

Therefore, the subject of the present invention is 10-1000.
in the range of nm, coated with a lamella coating and in the form of microparticles consisting of a polymer containing an oil phase,
The lamellar coating is characterized in that it has at least one silicone surfactant containing at least one oxyethylenated and / or oxypropyleneized chain.

The fine particles of the present invention are preferably 10-
The size is in the range of 600 nm.

Silicone surfactants are silicone compounds containing at least one oxyethylenated --OCH ₂ CH ₂ --and / or oxypropyleneated --OCH ₂ CH ₂ CH ₂ --chain. Examples of the silicone surfactant usable in the present invention include US Pat. No. 5,364,633,
And those described in US Pat. No. 5,411,744. These publications describe the use of silicone surfactants to prepare lipid vesicles. However, they are
It does not teach that such surfactants can form a lamellar phase around the microparticles.

Preferably, the silicone surfactant used in the present invention has the following formula (I):

Embedded image [In the above formula (I), R ₁ , R ₂ and R ₃ are independent of each other, and are a C ₁ -C ₆ alkyl group or a group (CH ₂ ) _{x-
(OCH 2 CH 2) y -} (OCH 2 CH 2 CH 2) a _z -OR _4, at least one of the radicals R _1, R ₂ or R ₃ is not an alkyl group; R ₄ is hydrogen, alkyl A group or an acyl group; A is an integer in the range of 0 to 200;
B is an integer in the range 0 to 50; A and B are not 0 at the same time; x is an integer in the range 1 to 6; y
Is an integer within the range of 1 to 30; z is an integer within the range of 0 to 5].

In a preferred embodiment of the present invention, the compound of formula (I) is a compound wherein the alkyl group is a methyl group, x is an integer in the range of 2 to 6, and y is an integer in the range of 4 to 30. Is.

As the silicone surfactant of formula (I),
The following formula (II):

Embedded image [In the above formula (II), A is an integer in the range of 20 to 105, B is an integer in the range of 2 to 10, and y is 10 to
Which is an integer within the range of 20].

Further, as an example of the silicone surfactant of the formula (I), the following formula (III):

[Chemical 6] The compound of [in the above formula (III), A ′ and y are integers within the range of 10 to 20] can be mentioned.

The compounds of the present invention include DC 5329, DC 7439-146, DC 2-56 from Dow Corning.
It is also possible to use those sold under the names 95 and Q4-3667. DC 5329, DC 7439-146 and DC 2-569
Compounds of the formula (II) are each represented by A
A is 22, B is 2, y is 12; A is 103, B is 10, y
Is 12; A is 27, B is 3, and y is 12.

The compound of Q4-3667 is the compound of formula (III) in which A'is 15 and y is 13.

The polymer constituting the fine particles of the present invention is
It may be a biodegradable or non-biodegradable polymer. Microparticles made from biodegradable polymers
While penetrating into the skin and being decomposed in the epidermis by the action of the enzymes present there, the microparticles made from a non-biodegradable polymer penetrate only the surface layer of the stratum corneum, Naturally emitted during regeneration.

As biodegradable polymers, it is possible to use any polymers which are degradable by skin enzymes, in particular the polymers described in EP-A-447318. As biodegradable polymers, in particular:
Mention may be made of poly-L-lactides, poly-DL-lactides and polycaprolactones.

As non-biodegradable polymers, those selected from all polymers which are not degraded by skin enzymes, in particular the polymers described in EP 557489 can be used. Non-biodegradable polymers may include, among others, copolymers of vinyl chloride and vinyl acetate, copolymers of methacrylic acid and methacrylic acid methyl ester.

Preferably, the microparticles of the present invention are nanocapsules. For this reason, the polymers mentioned above, in particular,
It is suitable for obtaining nanocapsules.

In the microparticles of the present invention, the weight ratio of silicone surfactant to polymer is advantageously 0.
It is within the range of 1 to 2, preferably 0.5 to 1.

The microparticles generally contain at least one entrapped active agent which either constitutes the oil phase itself or is contained in a carrier which constitutes the oil phase.

The weight ratio of polymer to activator and / or carrier is advantageously in the range 0.01 to 1, preferably 0.05 to 0.5.

The microparticles of the present invention can be prepared by conventional methods, in particular
European Patent Publication No. 447318 and International Patent Publication No. 9
It is prepared by the method described in 3/25195.

In some of these methods, surfactants are used during the manufacture of the microparticles. Surfactants which can be used in these processes are, for example, condensates of ethylene oxide and propylene oxide, in particular poloxamers, such as those sold by BASF under the name "Pluronic F-68". You can list what you have.

The coated microparticles according to the invention are used in compositions for topical application, in particular cosmetic and / or dermatological compositions.

The subject of the invention is also a composition, in particular a composition for topical application, characterized in that it comprises the abovementioned microparticles in a suitable medium.

The microparticles are generally mixed into the composition in suspension.

Suitable media are those used for the production of microparticles and / or media acceptable for topical application,
That is, it is understood to mean a medium which is compatible with the skin, mucous membranes, nails, scalp and hair.

Preferably, the microparticles are 0.1-40% by weight, more preferably 5-2, based on the total weight of the composition.
5% by weight.

In the composition of the present invention, the scavengable active agent can be any active agent which can have cosmetic and / or therapeutic activity. The active agent may be lipophilic or hydrophilic. Softeners, humectants, free radical scavengers, antioxidants, anti-inflammatory agents, vitamins, depigmenting agents, anti-acne agents, antiseborrheic agents, keratolytic agents,
Slimming agents, skin colorants, sunscreen agents, essential oils,
Pigments, sunburn accelerators, fragrances, colorants, melanin regulators, anti-wrinkle and anti-aging agents, lipid regulators, antibacterial agents, antifungal agents,
Antiperspirant, deodorant, immunomodulatory agent
s), cicatrizing agents, vascular protective agents, skin conditioning agents, and mixtures thereof.

In the nanocapsules, the active agent is preferably the lipophilic active agent, alone or dissolved in a lipophilic carrier, but can also be in the form of a dispersion, suspension or emulsion. it can. The oily carriers are preferably selected from unmodified or modified triglycerides, silicone oils, especially volatile silicone oils, and non-silicone oils, especially mineral oils. For example, an oily carrier can include caprylic acid / capric acid triglyceride.

In the nanocapsules of the present invention, as the entrapped active agent that can be used, in particular, an active agent conventionally used in the art, for example, vitamins such as tocopherol (vitamin E) and tocopherol acetate can be used. Derivatives such as retinol (vitamin A) and retinol palmitate, essential fatty acids, especially vitamin F; keratolytic agents such as salicylic acid and its derivatives, especially FR-A-258.
1542, EP 378936, and EP 570230, especially 5-n-octanoylsalicylic acid, 5-n-decanoylsalicylic acid, 5-n-dodecanoylsalicylic acid, 5 −
Mention may be made of n-octylsalicylic acid, 5-n-heptyloxysalicylic acid, and 4-n-heptyloxysalicylic acid.

The compositions of the invention may be in any form suitable for topical application, in particular solutions, water-in-oil or oil-in-water emulsions, or ionic and / or generally known as liposomes. It can take the form of an aqueous dispersion based on non-ionic lipid vesicles. For example, it can be serum, milk or cream.

Further, the composition of the present invention may be in the form of an oil-in-water type emulsion described in European Patent Publication No. 641557, in which oil droplets dispersed in water are lamellar coated.

The amounts of the different components of the composition of the invention are those traditionally used in the art.

When the composition according to the invention is an emulsion, the proportion of fatty phase is between 5 and 80 relative to the total weight of the composition.
%, Preferably in the range of 5 to 50% by weight. The oils, emulsifiers, and coemulsifiers used in the composition in the form of an emulsion are selected from those traditionally used in the art. The emulsifiers and coemulsifiers are in the range of 0.3 to 30% by weight, preferably 0.5 to 20% by weight, based on the total weight of the composition. The emulsion may further contain lipid vesicles.

In a known manner, the compositions according to the invention also contain the adjuvants customary in the field of cosmetics and / or dermatology, such as gelling agents, activators, preservatives, antioxidants, complexing agents. Agents, solvents, fragrances, fillers,
Sunscreen agents, bactericides, odor absorbers, and coloring agents may be included. The amounts of these different adjuvants are those traditionally used in the art, for example 0.01 to 20% relative to the total weight of the composition. Due to their nature, these adjuvants are introduced into the fat phase, the aqueous phase, and / or the lipid vesicles. Oils usable in the present invention include mineral oils (liquid paraffin), vegetable oils (avocado oil, sweet almond oil), animal oils, synthetic oils (stearyl heptanoate,
Caprin-caprylic acid triglyceride), silicone oils (volatile silicone oil, polydimethylsiloxane), and fluorinated oils can be mentioned. Furthermore, as the fatty substances, fatty alcohols (cetyl alcohol), fatty acids (stearic acid) and waxes may be used.

Examples of emulsifiers that can be used in the present invention include glycerol monostearate and oxyethylenated sorbitan monosterate.
arate), sucrose distear
ate) and cetearyl alcohol (cetearyl alco
Hol) polyethylene glycol ether can be mentioned.

Hydrophilic gelling agents include carboxyvinyl polymers (carbomer), acrylic acid copolymers, polyacrylamides, polysaccharides, natural gums, and clays, which are lipophilic. Gelling agents may include modified clays such as bentones, metal salts of fatty acids, ethyl cellulose, or polyethylene.

Polyols (glycerol), amino acids (hydroxyproline), water-soluble vitamins (D-panthenol), and polysaccharides (sodium hyaluronate) may be used as hydrophilic activators.

As lipophilic activators, retinol (vitamin A) and its derivatives (retinol palmitate) and tocopherol (vitamin E) and its derivatives may be used.

The composition according to the invention may be used for treating the skin, mucous membranes, nails, scalp, and / or hair, in particular for aging the skin (wrinkles, complexion). The subject of the present invention is therefore also the use of the compositions as described above in cosmetic and / or dermatological treatments for combating aging of the skin.

The subject of the invention is,
And / or mucous membranes, and / or nails, and / or scalp, and / or hair, characterized in that it comprises skin and / or mucous membranes, and / or nails, and / or scalp, and / or Or in the non-therapeutic beauty method of hair.

[0045]

EXAMPLES The following examples of compositions of the invention are provided by way of illustration and not limitation of the invention. In addition, here, the amount is represented by% by weight.

Example 1 Preparation of Coated Nanocapsules of the Invention Containing 5% Tocopherol Acetate In a 500 ml beaker, 1 g polycaprolactone, 5 g tocopherol acetate, and 1 g DC 2-569.
5 was dissolved in 200 ml of acetone with gentle stirring. In another beaker, 0.5 g of Pluronic
F-68 was dissolved in 200 g of distilled water with stirring. The acetone phase was then poured into the aqueous phase with stirring. Then, acetone and a part of water were evaporated by a rotary evaporator until 100 ml of a solution was obtained, whereby a suspension of nanocapsules having an average diameter of 300 nm was obtained.

Example 2 Preparation of Coated Nanocapsules of the Invention Containing 2.5% Retinol Palmitate 5 g of a mixture containing retinol palmitate and capryl / capric triglyceride in the same proportions instead of tocopherol acetate. The same procedure as in Example 1 was carried out except that was used.

Comparative Example : Preparation of Conventional Coated Nanocapsules Containing 5% Tocopherol Acetate Instead of 5 g of tocopherol acetate, DC 2-5695,
The procedure was as in Example 1, except that 1 g of lecithin was used.

The nanocapsules obtained in Example 1 were compared with those obtained in Comparative Example. The results are shown in the following table.

[0050]

[Table 1]

These results show that the coatings obtained with the silicone surfactants according to the invention are leak-free, as good as conventional coatings, without oxidation. Further, the nanocapsules coated with the surfactant of the present invention are more than conventional nanocapsules.
Prepared early.

Example 3: Cream for skin care- Nanocapsules obtained in Example 10% Fat phase: -Ceteareth-33 (Cetearyl alcohol polyethylene glycol ether) 0.4% -Monostearine. Glycerol 0.8% -Polydimethylsiloxane 0.6% -Caprin / caprylic triglyceride 10% -Liquid paraffin 6% -Cetyl alcohol 0.6% Aqueous phase: -Preservative 0.3% -Demineralized water 100 total Amount to be%

The procedure for preparing this cream is as follows: the fat phase and the water phase are brought separately to 80 ° C., then the fat phase is put into the water phase with vigorous stirring, the temperature of the mixture being 5
Stirring was continued until it reached 0 ° C. Then, the mixture was further slowly stirred until the temperature of the mixture reached 30 ° C. Then, the suspension of the nanocapsules of Example 1 was added with slow stirring.

The daily application of the resulting white cream was able to improve the complexion of the facial skin.

Example 4: Face Day Cream Phase A: 1.75% sucrose distearate-oxyethylenated sorbitan stearate [Tween 61] sold by ICI 1.15. % -Stearic acid 0.75% -Stearyl heptanoate 4% -Liquid paraffin 1.5% -Avocado oil 3% -Sweet almond oil 3% -Volatile silicone oil 2.5% -Retinol palmitate, 1500 IU / mg 0.5% -preservative 0.2% Phase B: -Glycerol 5% -Triethanolamine 0.35% -Demineralized water 58.3% Phase C: -Suspension of nanocapsules of Example 1 10% D Phase: -Carbomer 0.3% -Demineralized water 7.7%

The resulting cream containing coated nanocapsules further contains oil droplets with a lamella coating as described in EP 641557.

The procedure for preparing this cream is as follows: The ingredients of phase A are mixed and the mixture is heated to 60 ° C;
Phase B was treated in the same manner; then, with stirring, phase B was added to phase A; the resulting mixture was continuously applied three times at 500 bar (5 × 10 ⁷ Pa) in a high pressure homogenizer. ,
Homogenized. The mixture was then brought to room temperature and phase C was added with gentle stirring. Phase D was carefully added and gently mixed until the components were evenly dispersed.

The cream obtained is shiny, smooth and has a very good white texture, which is applied daily to improve the complexion,
And it became possible to treat wrinkles.

Example 5: Serum against aging (composition containing liposomes) Phase A: -Sorbitan palmitate [Span 40 sold by ICI, 0.475% -Cholesterol 0. 475% -N-stearoyl glutamic acid monosodium salt [Acylglutamate HS 11 sold by Azinomoto] 0.05% Phase B: -Demineralized water 15% -Glycerol 3% -Hydroxyproline 1% Phase C: -Deionized water 52.9% -Preservative 0.3% -D-Panthenol 1.5% -Sodium hyaluronate 0.1% Phase D: -Suspension of nanocapsules of Example 2 15% Phase E: -Carbomer 0.2% -Triethanolamine 0.2% -Demineralized water 9.8%

The procedure for preparing this cream is as follows: Phase A was mixed with Phase B which had been preheated to 80 ° C. and stirred for 1 hour or more. The mixture was then homogenized in a high pressure homogenizer at 600 bar (6 × 10 ⁷ Pa) for 3 consecutive times. The mixture was brought to room temperature and phase C was added with gentle stirring. Phase D was then carefully added and gently mixed until the components were evenly dispersed. Finally, phase E was added slowly and stirring continued until the mixture was completely homogenous.

A serum was obtained which had a fairly fresh feel on application.

Claims (22)

[Claims] 1. In microparticles coated with a lamellar coating and consisting of a polymer containing an oil phase, in the size range of 10 to 1000 nm, said lamellar coating comprising at least one oxyethylenated and / or oxypropylene. Microparticles, characterized in that they consist of at least one silicone surfactant containing modified chains. 2. A silicone surfactant has the following formula (I): [In the above formula (I), R ₁ , R ₂ and R ₃ are independent of each other, and are a C ₁ -C ₆ alkyl group or a group (CH ₂ ) _{x-
(OCH 2 CH 2) y -} (OCH 2 CH 2 CH 2) a _z -OR _4, be at least one alkyl group of R _1, R ₂ or R _3; R ₄ is hydrogen, an alkyl group Or an acyl group; A is an integer in the range of 0 to 200; B
Is an integer in the range 0-50; A and B are not 0 at the same time; x is an integer in the range 1-6; y
Is an integer within the range of 1 to 30; z is an integer within the range of 0 to 5], and the fine particles according to claim 1. 3. The silicone surfactant has an alkyl group as a methyl group, x is an integer in the range of 2 to 6, and y
Is a compound of formula (I), wherein is an integer in the range of 4 to 30; 4. The silicone surfactant has the formula (I
I): embedded image [In the above formula (II), A is an integer in the range of 20 to 105, B is an integer in the range of 2 to 10, and y is 10 to
It is an integer within the range of 20], The fine particle of any one of Claim 1 thru | or 3 characterized by the above-mentioned. 5. A silicone surfactant, wherein A is 22, B
Is 2, y is 12; A is 103, B is 10, y is 12; A
Is 27, B is 3 and y is 12 selected from the compounds of formula (II). 6. The silicone surfactant has the formula (II)
I): The fine particles according to any one of claims 1 to 5, wherein A'and y in the above formula (III) are integers within the range of 10 to 20. 7. The silicone surfactant has A ′ of 15,
Microparticle according to claim 6, characterized in that it is a compound of formula (III) wherein y is 13. 8. The microparticles according to claim 1, which have a size within a range of 10 to 600 nm. 9. The polymer comprises poly-L-lactides, and poly-DL-lactides, polycaprolactones,
9. A vinyl chloride / vinyl acetate copolymer or a methacrylic acid / methacrylic acid methyl ester copolymer.
The microparticle according to the item. 10. The microparticle according to any one of claims 1 to 9, wherein the polymer is a biodegradable polymer. 11. The microparticle according to any one of claims 1 to 10, which is a nanocapsule. 12. Microparticles according to any one of the preceding claims, characterized in that the weight ratio of silicone surfactant to polymer is in the range 0.1-2. 13. Microparticle according to any one of claims 1 to 12, characterized in that it contains at least one active agent. 14. The weight ratio of polymer to active agent is:
It is within the range of 0.01 to 1.
The fine particles according to item 3. 15. Microparticles according to claim 13 or 14, characterized in that the active agent is a lipophilic active agent. 16. The activator is retinol (vitamin A).
The microparticle according to any one of claims 13 to 15, which is selected from the group consisting of: and a derivative thereof, and tocopherol (vitamin E) and a derivative thereof. 17. A composition for topical application, characterized in that the fine particles according to any one of claims 1 to 16 are contained in a suitable medium. 18. The microparticles are 0.1-40% by weight, based on the total weight of the composition.
A composition according to claim 1. 19. The method according to claim 17, which is in the form of a dispersion liquid or an emulsion of lipid vesicles.
9. The composition according to 8. 20. The composition according to claim 17, which is a cosmetic and / or dermatological composition. 21. The composition according to claim 17, which is used for cosmetically and / or dermatologically treating skin aging. 22. Application of the composition according to claim 17 to the skin and / or the mucous membranes and / or the nails and / or the scalp and / or the hair. Non-therapeutic cosmetic method of skin and / or mucous membranes and / or nails and / or scalp and / or hair.